CN1085700C - Random copolymer compositions - Google Patents
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- CN1085700C CN1085700C CN94194174A CN94194174A CN1085700C CN 1085700 C CN1085700 C CN 1085700C CN 94194174 A CN94194174 A CN 94194174A CN 94194174 A CN94194174 A CN 94194174A CN 1085700 C CN1085700 C CN 1085700C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Abstract
A polymer composition having improved balanced mechanical and optical properties comprising (1) a random copolymer comprising from about 0.8 % to about 20 % by weight of butene-1 and from about 80 % to about 99.2 % by weight of propylene, and (2) from about 0 %-0.35 % by weight of polymer composition of a synthetic amorphous silica antiblock agent.
Description
Technical field
The present invention relates to have improved optical property, be applicable to and make the composition that the low film of hexane extraction thing content contains the random copolymers of propylene and butene-1.The invention still further relates to and be applicable to that the manufacturing tensile property is good, and the propylene of the alignment films of excellent optical performance (for example low haze and low yellowing) and the random copolymers of butene-1.
Technical background
Because the polymkeric substance cost is lower and show satisfied performance, olefin polymer compositions is being welcome widely aspect many commercial uses and is being used.Comprise plastics film in these commercial uses, for example casting films and alignment films.Plastics film can be used for food and commodity packaging, foodstuff container and medical apparatus, as syringe.For the material as food product pack, medical apparatus and other commerical prods, whether its very important requirement is to have impurity or foreign matter (as bits) just can judge from the outside in the thing in the container.If to change then be undesirable to the color of content material when seeing through container and observing from the outside.Based on such reason, wish that in these Application Areass the polymer composition that uses has high-clarity, high gloss and suitable color.And in recent years, thin film industry just constantly claims, and wishes that polymer composition has improved tensile property so that improve workability.
It is reported, for the homopolymer that is able to take industrial stretching ratio product is provided, knownly noncrystalline the or solubles content of homopolymer can be adjusted into 6.0% (weight) from 4.2% (weight).It is low that the tensile strength of the polymkeric substance that this content of amorphous is higher remains for ethylene atactic copolymer.The ethylene atactic copolymer that contains ethene 0.3%～0.7% (weight) typically is used for orientation (gather) propylene film so that well balanced between acquisition processibility and the mechanical property.When ethene add-on during greater than 0.5% (weight), the product of often producing is low and softer because of tensile modulus.And the ethylene random film usually manifests aged outward appearance vestige, " greasy " or " hazing " layer that produces gradually at film surface for example, and this transparency for film has adverse influence.
Anti typically is used for the caking (or stick together) of polymeric film to prevent polymeric film always.But this class anti is to the optical property of polymeric film, such as mist degree and gloss, and adverse influence is arranged.
The multipolymer that hexane extraction thing content is low is well, because U.S. food and FAD (" FDA ") have the requirement of the concrete soluble matters that must satisfy to the polyolefin copolymer that is used for food and medical use.As noted earlier, ethylene atactic copolymer typically is used for food and drug packaging.But ethylene atactic copolymer must have additional washing step could satisfy the hexane extraction thing restriction of FDA in the mill.
The method that if improved random copolymers and film thereof can be provided and produce the improved multipolymer of this kind, make it to have favorable optical performance, as low haze, low haze, good color, low yellowing, and between low hexane extract, low xylene solubles level, improved tensile strength and the high rigidity improved balance before being arranged, then will be a good thing.
EP-A-450,456 disclose and are not having under the condition of liquid, do not have to utilize Ziegler-Natta catalyst under the situation of monomer condensation the propylene that can make by vapour phase polymerization and the multipolymer of alpha-olefin in the gas space.The intrinsic standoff ratio of propylene and 1-alkene is 5: 1-100: 1.
GB-A-2,105,651 disclose a kind of polypropylene film, this film comprises crystalline polypropylene/alpha-olefin or crystalline polypropylene/alpha-olefin/ethylene copolymer layer, xylene soluble polymkeric substance when wherein containing 10-30% (weight) C4-18 alpha-olefin, 0-5% (weight) ethene and 10% (weight) or still less 20 ℃.Described and contained 0.5% or the multipolymer of more silicone-type release agent.
Polypropylene film based on metallizing can be consulted JP-A-3, and 031,344 and EP-A-99,251.
Of the present invention open
The present invention relates to a kind of equilibrated polymer composition between improved machinery and the optical property that has.More specifically say, the invention provides a kind of polymer composition, wherein comprise (i) a kind of random copolymers, the propylene that contains the butene-1 and 80%～99.5% (weight) of 0.5%～20% (weight), and (2) account for synthetic amorphous (being amorphous) silicon oxide antiblocking agent of polymer composition 0%～0.35% (weight), its bulk density is between 300～360g/l, and its oil absorption rate is between 80～100g/100g; Wherein this polymer composition has following feature:
(a) 5.5 (the pressing 21.C.F.R.177.1520 (C) (3.2)) at the most of the hexane extraction thing 50 ℃ the time.
(b) mist degree (pressing ASTM D-1003 measures) maximum 5%
(c) xylene solubles thing level the highest by 13% (pressing 21.C.F.R.177.1520 measures) 23 ℃ the time,
(d) tensile modulus at least 8812 (7031) kg/cm
2(40,000 (100,000) psi) (press ASTM D 882 (1% secant is under 0.13 centimeters/minute (0.05 inch per minute) condition), and
(e) extension at break (pressing ASTM D 882 measures) is between 80%～2000%.
In a specific embodiments, this multipolymer contains 0.8%-20% (weight) butene-1 and 80%-99.5% (weight) propylene.
The present invention also is provided at the method that this random copolymer composition is produced down in a kind of existence of high reactivity stereospecific catalyst system, and this catalyst system is that the contact by following component obtains: (i) a kind of olefinic polymerization raw catalyst and (ii) a kind of organoaluminum promotor and (iii) a kind of selective control agent.
In addition, the present invention relates to a kind of film product, it comprises orientation bottom and the polymer layer on the one side at least of this random copolymers bottom that is made of random copolymer composition.The present invention also provides a kind of random copolymers film that metal plating is arranged.
Implement best mode of the present invention
Polymer resin composition of the present invention can be by allowing propylene and butene-1 under polymerizing condition and a kind of titanium base olefin polymerization catalyst system, carries out polymerization under for example a kind of existence of the polymerisation catalyst system that contains magnesium and titanium and obtain.This kind polymerisation catalyst system generally is that the combination by the catalyst based component of halogenated titanium, organo-aluminium compound and one or more electron donor(ED)s obtains.For the purpose of explanation, this paper claims solid-state titanium-containing catalyst component to be " raw catalyst ", and organo-aluminium compound is " promotor ", and the electronic donor compound capable that uses separately then is called as " selective control agent " (SCA) usually.
Though there are various chemical compounds to can be used to produce raw catalyst, but typical raw catalyst of the present invention be by in the presence of halohydrocarbon and electron donor(ED) with halogenated tetravalent titanium compound with formula M gR ' R " the magnesium compound halogenation make; wherein R ' is alkoxyl group or aryloxy, and R " is alkoxyl group, alkyl carbonate, aryloxy or halogen.
Used magnesium compound contains alkoxyl group, aryloxy, alkyl carbonate or halogen in the preparation of this solid catalyst component.When containing alkoxyl group, this alkoxyl group generally contains 1～10 carbon atom.The alkoxyl group that contains 1～8 carbon atom is preferably, and the alkoxyl group that contains 2～4 carbon atoms is then better.This aryloxy contains 6～10 carbon atoms usually when containing aryloxy, and serves as better with 6～8 carbon atoms.When containing the alkyl carbonate, it contains 1～10 carbon atom usually.When containing halogen, then preferred bromine, fluorine, iodine or chlorine, and wherein better with chlorine.
Suitable magnesium compound is magnesium chloride, bromination magnesium ethylate, chlorination isobutoxy magnesium, iodate phenoxy group magnesium, magnesium fluoride, bromination cumyloxy base magnesium, diethoxy magnesium, isopropoxy magnesium, Magnesium Stearate, ethyl carbonate magnesium and chlorination naphthyloxy magnesium.Preferred magnesium compound is a diethoxy magnesium.
Typically adopt excessive titanium compound to realize the magnesium compound halogenation with halogenated tetravalent titanium compound.Usually, every mole of magnesium compound should use at least 2 moles of titanium compounds.Every mole of more handy 4～100 moles of titanium compounds of magnesium compound, and preferably every mole of magnesium compound with 8～20 moles of titanium compounds.
Can realize that better this temperature is between 70 ℃～120 ℃ by allowing these compounds under the temperature of 60 ℃～150 ℃ rising, contact with halogenation tetravalent titanium compound halogenated magnesium compound.Usually allow reaction carry out 0.1～6 hour, better carried out 0.5～3.5 hour.Halogenated products is a kind of solid matter, can it be separated from liquid reaction medium by filtration, decantation or other suitable methods.
Being used for the halogenation tetravalent titanium compound of halogenated magnesium compound contains at least 2 halogen atoms usually, and preferably contains 4 halogen atoms.This type of halogen atom is chlorine atom, bromine atoms, iodine atom or fluorine atom.Like this, the halogenation tetravalent titanium compound just contains at the most 2 alkoxyl groups or aryloxy.The example of suitable halogenation tetravalent titanium compound comprises halogenated alkoxy titanium, dibrominated diethoxy titanium, triiodide titanium isopropoxide, dichloride two hexyloxy titaniums and tri-chlorination phenoxide titanium, and titanium tetrahalide, for example, and titanium tetrachloride and titanium tetrabromide.Preferred halogenation tetravalent titanium compound is a titanium tetrachloride.
The suitable halohydrocarbon that may exist comprises aromatics or aliphatic series (comprising cyclic hydrocarbon and alicyclic hydrocarbon) compound.This halohydrocarbon better contains 1 or 2 halogen atom, but the words of wishing also can contain more a plurality of.Preferably, this halogen is chlorine, bromine or fluorine independently.The example of suitable aromatic halohydrocarbons is chlorobenzene, bromobenzene, dichlorobenzene, dichloro dibromobenzene, ortho-chlorotolu'ene, toluene(mono)chloride, toluene dichloride, chloronaphthalene.Chlorobenzene, ortho-chlorotolu'ene and dichlorobenzene are halohydrocarbon preferably, serve as better with chlorobenzene and ortho-chlorotolu'ene again wherein.
The aliphatic halogenated hydrocarbons that is suitable for better contains 1～12 carbon atom.Better this kind halohydrocarbon has 1～9 carbon atom, and 2 halogen atoms should be arranged at least.Preferably this halogen atom is a chlorine.Suitable aliphatic halogenated hydrocarbons comprises methylene bromide, trichloromethane, 1,2-ethylene dichloride, trichloroethane, chloro fluoroethane, hexachloroethane, trichloropropane, chlorobutane, dichlorobutane, chloropentane, three chloro-fluoro-octanes, tetrachloro octane-iso, dibromo difluoro decane.Preferred aliphatic halogenated hydrocarbons is tetracol phenixin and trichloroethane.
Aromatic halohydrocarbons is preferred, 6～12 carbon atoms particularly, and those aromatic halohydrocarbons of 6～10 carbon atoms preferably.
Suitable inertia hydrocarbon diluent comprises aromatic hydrocarbon, for example the compound that is in a liquid state at normal temperatures of toluene, o-Xylol, m-xylene, p-Xylol, benzene, ethylbenzene, propyl benzene (as isopropyl benzene or claim cumene), Three methyl Benzene.
The electron donor(ED) that is fit to be included in the raw catalyst can be that conditional electronic used in the titanium base olefinic polymerization raw catalyst is given body, comprises ether, ester, ketone, amine, imines, nitrile, phosphine, ladder, arsine, alcoholate.Electron donor(ED) is an ester preferably, especially the aliphatic ester of aromatic monocarboxylate or dicarboxylic acid.The example of this better electron donor(ED) is methyl benzoate, ethyl benzoate, ethyl p-ethoxybenzoate, ethyl p-methyl benzoate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, terephthalic acid diisopropyl ester and naphthalene dicarboxylic acids dimethyl ester.This electron donor(ED) is the simplification compound or the mixture of two or more compounds, but better is that this electron donor(ED) is the simplification compound.Give in the body at ester electron-like preferably, ethyl benzoate and diisobutyl phthalate are good especially.Competent electron donor(ED) should be provided so as the mol ratio that makes electron donor(ED) and magnesium in the raw catalyst in 0.002～0.3 scope.The mol ratio that better is electron donor(ED) and magnesium in the raw catalyst and serves as better with 0.03～0.16 mol ratio between 0.03～0.2.
After solid-state halogenated products was separated from liquid phase reaction medium, available other halogenation tetravalent titanium compound was handled one or many to it.Be preferably, handle this halogenated products repeatedly with independent many parts halogenation tetravalent titanium compound.If halogenated products handles twice with independent many parts halogenation tetravalent titanium compound, then can obtain effect preferably.As first halogenation, common every mole of magnesium compound should use at least 2 moles of titanium compounds, and 4～100 moles of titanium compounds of better every mole of magnesium compound use, and preferably every mole of magnesium compound uses 4～20 moles of titanium compounds.
It is identical to handle the condition of using during the halogenation of the employed reaction conditions of this solid-state halogenated products with first magnesium compound with titanium compound.
Randomly, the halogenation tetravalent titanium compound with additional quantity wash solid-state halogenated products at least once after, handle this solid-state halogenated products at least once with one or more acyl chlorides.Suitable acyl chlorides comprises Benzoyl chloride and phthalyl chloride.Preferred acyl chlorides is a phthalyl chloride.
Solid-state halogenated products is after extra halogenation tetravalent titanium compound is handled one or many, it can be separated from liquid reaction medium, the inertia hydro carbons of 10 carbon atoms washs at least once to remove unreacted titanium compound with containing at the most, and is dry then.The example of the inertia hydro carbons that is suitable for washing is iso-pentane, octane-iso, hexane, heptane and hexanaphthene.
The titanium content of final washing after product is generally 1.5% (weight)～6.0% (weight), is preferably 2.0% (weight)～4.0% (weight).The atomic ratio of titanium and magnesium is typically between 0.01: 1～0.2: 1, preferably between 0.02: 1～0.1: 1 in the final product.
Promotor can be a kind of basic aluminum compound that has, and it is optional from the aluminum-based co-catalyst of using with titanium base raw catalyst traditionally.The example of organo-aluminium compound is trialkyl aluminium compound, alkoxyalkyl aluminum compound and halogenated alkyl aluminum compound, and wherein each alkyl contains 2～6 carbon atoms independently.Organo-aluminium compound is not halogen-containing preferably, and especially good be trialkyl aluminium compound, for example triethyl aluminum, triisobutyl aluminium, triisopropylaluminiuand and diethylhexyl aluminium.Triethyl aluminum is particularly preferred.The consumption of promotor generally will be enough to make the ratio of aluminium atom in the raw catalyst and titanium atom between 1: 1～300: 1, but preferably between 10: 1～100: 1.
The consumption of organoaluminum promotor generally should be enough to make every mole of titanium in the raw catalyst that 1 mole～about 150 moles, of aluminum per mole of titanium metal are arranged.Be preferably, the content of this promotor should be enough to make that every mole of titanium has 10 moles～about 100 moles aluminium in the raw catalyst.
The selective control agent that is used to prepare olefin polymerization catalysis is that those are used for uniting with titanium base raw catalyst and organoaluminum promotor the compound of use traditionally.Suitable selective control agent comprises the above-named electron donor(ED) that raw catalyst is produced that is used for, and still also includes organic silane compound, for example has the alkylalkoxy silane and the alkoxy aryl silane of following formula,
R '
rS
i(OR)
4-rWherein R ' is the alkyl or aryl that contains individual carbon atom 32 (comprising 32) at the most, and R is that the low alkyl group and the r that contain 4 carbon atoms at the most are 0～3.
The example of the selective control agent that is suitable for is an ester, for example ethyl p-ethoxybenzoate, diisobutyl phthalate, ethyl benzoate and ethyl p-methyl benzoate, and organosilane, for example second, isobutyl dimethoxy silane, n-propyl Trimethoxy silane, sec.-propyl Trimethoxy silane, ethyl triethoxysilane, octadecyl triethoxyl silane, octadecyl Trimethoxy silane and cyclohexyl methyl dimethoxy silane.The consumption of selective control agent should be enough to typically make that every mole of titanium has 0.01 mole～100 moles control agents in the former compound.Be preferably, provide enough selective control agents to make that every mole of titanium has 0.5 mole～70 moles control agents in the raw catalyst, and serve as better with 8 moles～50 moles.
The mode that solid-state raw catalyst precursor, titanic halogenide, optional inert diluent contact with electron donor(ED) is important, but is not crucial, and is typically traditional.In one embodiment, the raw catalyst precursor mixes with titanic halogenide, adds electron donor(ED) then in the mixture that forms.In another embodiment, electron donor(ED) and raw catalyst precursor mix with the mixture of titanic halogenide or titanic halogenide and the inert diluent of choosing wantonly, allow the solids that generates contact one to multiple time with the mixture of the thinner of choosing wantonly with titanic halogenide or titanic halogenide more then.The first contact of the inert diluent mixture of electron donor(ED), raw catalyst precursor and titanic halogenide or titanic halogenide/optional is suitable under the temperature of normal temperature～150 ℃ and is carried out.If with the heating of these materials, and initially contact temperature and be preferably 70 ℃～130 ℃, more preferably 75 ℃～110 ℃, then can obtain the better interaction between these materials.
In each and the halid contact process of titanic, randomly have the part inert diluent in the presence of, and react and contain solid carboxylic acid halides in some cases, and quicken as the further existence of Benzoyl chloride or phthalyl chloride.This solid-state raw catalyst (what obtain usually is spheroidal particle) typically finally washs with the unreactive hydrocarbons of 10 carbon atoms at the most, and dry and made with extra care under nitrogen.The example that is applicable to the inertia hydro carbons of washing is iso-pentane, octane-iso, hexane, heptane and hexanaphthene.
Which kind of polymerization process not to be crucial for enforcement of the present invention with specifically, therefore being regarded as traditional polymerization process at present all is applicable to method of the present invention.Polymerization is at the gas phase process of liquid phase process or employing fluid catalyst beds or adopts under certain polymerizing condition that condenses monomeric gas phase process and carry out.
The general inertia liquid diluent that adopts a kind of as the reaction diluent adding of the polymerization of carrying out in liquid phase perhaps contains the liquid diluent that polymeric alkene (being propylene and butene-1) takes place with another.Typical reaction conditions comprises: temperature of reaction is from 25 ℃～125 ℃, and better 35 ℃～100 ℃ be best with 75 ℃～90 ℃ especially, and pressure should be enough to reaction mixture is remained in the liquid phase.This pressure typically is 1034KPa (150psi)～8274KPa (1200psi), serves as preferred with the pressure of 1724KPa (250psi)～6205KPa (900psi).Liquid phase reaction can by intermittent mode, continuously or half-continuous process carry out.After the reaction, polymerisate can adopt traditional method to be reclaimed.The accurate control of the polymerizing condition of liquid phase process and reaction parameter then belongs to this professional known technology.
As another embodiment of the invention, polymerization can be carried out in the presence of fluid catalyst beds by gas phase process.People's such as Goeke U, S. patent 4,379,759 (receipts are made the reference of this paper) has been described a kind of like this gas phase polymerization technology, and it relates to fluidized-bed and gas-phase reaction.Gas phase process typically is included in the preliminary shaping polymer beads of the some amount of packing in the reactor and the catalyst component of lesser amt.Wanting polymeric alkene, promptly propylene and butene-1 sent particle layers with the speed that is enough to initiated polymerization.The mol ratio of butene-1 and propylene is generally 0.01～0.30 in the gaseous mixture.In the time will making the random copolymer of the butene-1 that contains 0.5%～6.5% (weight) butene-1 and propylene, the mol ratio of butene-1 and propylene is typically 0.01～0.13 in the gas phase, is preferably 0.02～0.12, and serves as better with 0.06～0.08.
After grain bed, unreacting gas is extracted out from reactor and returned together with adding feeding gas.Along with catalyzer loses owing to carrying the minority catalyzer in the polymerisate secretly, can provide extra catalyzer to reactor, this usually is by adopting the inertia carrying agent, waiting as mineral oil, nitrogen or argon gas and realize.Temperature of reaction is chosen in below the polymer beads sintering temperature, and can control by the external heat exchanger in the gas circulation loop.Temperature of reaction typically is 30 ℃～90 ℃, and 50 ℃～85 ℃ temperature of reaction is then better, and 50 ℃～70 ℃ better, and 55 ℃～65 ℃ be best.Reaction pressure is up to 4137KPa (600psi) usually, but reaction pressure from 552KPa (80psi) to 4137KPa (600psi) better, and is best with 2068KPa (300psi) to the reaction pressure of 2758KPa (400psi).Then all belong to thing in the known technology scope as for the problems such as circulation of the adding of the accurate control of reaction conditions and catalyzer and feeding gas and unreacted monomer.
No matter be liquid phase or gas-phase polymerization processes, all can in reaction mixture, add molecular hydrogen as the molecular weight of chain-transfer agent with conditioned reaction device polymerisate.The accurate control of reaction conditions and the adding speed of feed component and molecular hydrogen all completely belong to the content in the known technology scope.
The particulate materials that forms by growing polymer on the polymer beads that provides to fluidized-bed is provided ideal reactor polymerisate, perhaps obtains as the particle that generates in reactor.Polymer beads is taken out with the speed that roughly is equivalent to the polymkeric substance generation from reactor, and this particle is delivered to down road reaction zone or it is refining with traditional method, again for using.
The polymkeric substance of producing is a random copolymers, and it structurally generally is mainly isotaxy.Better this random copolymers at least 70% is isotactic structurally, especially at least 85%.For the catalyst amounts of using, the productive rate of polymkeric substance is high.This random copolymers can be the binary random copolymer of 1-butylene and propylene.
In first specific embodiments of the present invention, butene-1 content is 0.5%～6.5% in the polymer composition, is preferably 0.8～5.5%, more preferably 1%～5%, and be preferably 1.3%～3% (weight).This polymer composition has one or more features in following (A)～(H):
(A) mist degree (pressing ASTM D-1003 measures) is the highest by 3.0%, better the highest by 2.0%, better the highest by 1.5%, and preferably is up to 1.0%.Mist degree (muddy degree or milky white degree) is the tolerance of transparency, and weighs with light transmission percentage ratio.If the granularity of silicon oxide is greater than light wavelength, the existence that then resembles the various additives of silicon oxide and so on has adverse influence to haze value.And the thickness of film also influences haze value, and for example along with film thickness increases, haze value also increases;
(B) hexane extraction thing content 50 ℃ the time, (measuring) according to 21 C.F.R.177.1520 (C) (3.1 and 3.2), at the most 2.6%, better at the most 2.0%, and better at the most 1.5%;
(C) xylene soluble part level 23 ℃ the time, (measuring) according to 21 C.F.R.177.1520, at the most 6%, better 5.5%, better at the most 4.5%.The xylene soluble part mainly is made of amorphous (atactic) polymkeric substance and semi-crystalline polymer;
(D) tangent modulus is (according to ASTM D 882 (1% secant is under 0.13cm/ branch (0.05 inch per minute)), at least 14,060kg/cm
2(200,000psi), better at least 21,100kg/cm
2(300,000psi), better at least 26,400kg/cm
2(375,000psi);
(E) fusing point is 144 ℃～158 ℃, and better 148 ℃～158 ℃, better 152 ℃～158 ℃;
(F) gloss (pressing ASTM D-523,60 ℃ of mensuration) is 140～155, is preferably 143～150; Best 145～150;
(G) tensile strength (measuring machine direction (MD)), 1195kg/cm at least according to ASTM D 638
2(17,000psi), better 1547kg/cm at least
2(22,000psi), and best 1758kg/cm at least
2(25,000psi); And
(H) extension at break, 80%～200%.
When adopting typical gas phase process to produce, and the melt flow of this random copolymers (represent with dg/min, by conventional test methodologies, ASTM-1238 for example, condition L measures) be generally 1～4, better 1.5～3.9, better 2.0～3.0.Along with the raising of melt flow, the optical property of random copolymer composition will improve.
According to a concrete aspect of first embodiment of the invention,, for example more than 180 ℃, use the peroxide treatment random copolymer resin at high temperature.This peroxide treatment process (also being " visbreaking ") belongs to this professional known technology fully, and can be used for adjusting as required the melt flow of polymerisate in the reactor.
Being used for visbroken polymers product of the present invention can be by carrying out visbreaking and obtain having at least the polymer composition of the present invention of the melt flow of 1.5dg/min.The melt flow of the visbreaking product that obtains and the starting polymer product of visbreaking not is than being at least 1.5, better at least 2.0, better at least 2.5.
The feature of the polymer composition of this specific embodiments of the present invention and visbreaking derivative thereof is improved low heat seal initial temperature, low hexane extraction, good stiffness and favorable optical performance, for example the balance between low haze, low yellowing and low haze etc.
Another concrete aspect according to first specific embodiments of the present invention, said composition comprises an additive-package, wherein comprise 0.04%～0.06% (weight) four-[methylene radical (3,5-di-t-butyl-4-hydroxyl hydrogenation cinnamic ester)]-methane, 0.05%～0.11% (weight) two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites and 0.01%～0.04% (weight) hydroxide carbonic acid magnalium hydrate, more than every kind be benchmark all with the multipolymer gross weight.
The composition of first specific embodiments can be by the traditional method that is used to produce biaxially oriented polypropylene film, and for example plane double shaft stretches or tubulose is biaxial stretch-formed etc., further processes.The tensile temperature can be from the room temperature to the multipolymer fusing point, better 130 ℃～155 ℃.Stretch ratio wishes to be at least 2: 1, better at least 5: 1, better at least 6: 1, preferably at least 9: 1.
According to first specific embodiments of the present invention on the other hand, when producing film laminates, this random copolymers has a heat sealable polymer layer as bottom at least one outside surface of this bottom.This bottom and polymer layer can be coextrusion.Can comprise " sandwich " method of knowing with other method, be thermally bonded to ready made polymer layer on this bottom this moment.
This heat sealable polymkeric substance surface layer can be transformed by following material, for example ethylene-propylene-butene-1 terpolymers, second-third (EP) random copolymers, propene-1-butene-1 multipolymer, ethene-1-Butylene copolymer or above-mentioned blend.Suitable terpolymer comprises by following component and obtaining through random mutual copolymerization: 1%～8% (weight) ethene, better 3%～5% (weight) ethene, with 65%～95% (weight) propylene, better 86～93% (weight) propylene reaches the butene-1 of representing rest part.The melting index of these terpolymers in the time of 230 ℃ is generally 2～7, and with 3～7 more favourable, its crystalline melt point is 100 ℃～130 ℃, molecular-weight average 25,000～100,000, density 0.89～0.92g/cm
3
The EP random copolymers that is applicable to heat sealable polymkeric substance surface layer generally contains 2% (weight)～7% (weight) ethene, and all the other are propylene, and the melting index in the time of its 230 ℃ is generally in 2～7 scope, and serves as better with 3～8.Crystalline melt point is generally 125 ℃～140 ℃, and number-average molecular weight is 25,000～100,000.Density is generally 0.89～0.92g/cm
3
Be applicable to that propene-1-butene-1 multipolymer of heat sealable polymkeric substance surface layer generally contains the butylene of 7.0% (weight)～15% (weight), all the other are propylene.The feature of this propene-1-butene-1 multipolymer is: (a) heat seal initial temperature is low, and for example 105 ℃～140 ℃, better 105 ℃～110 ℃; (b) mist degree is not higher than 6%, better is not higher than 4%; (c) modulus (pressing ASTM D 882 measures), 4218kg/cm at least
2(60,000psi), better 5625kg/cm at least
2(80,000psi); And (d) hexane extraction thing (measuring by 21 CFR 177 1530 (c) (3.1 and 3.2)) 50 ℃ the time, at the most 5.5%, better 3.5%, better at the most 2.6%.
Generally, when making heat sealable polymkeric substance surface layer with the blend of terpolymer and random copolymers, this blend should contain 10%～90% (weight) ter-polymers, and the ter-polymers of better 40%～60% (weight), and all the other are random copolymers.
By first specific embodiments of the present invention on the other hand, this random copolymer composition is suitable for carrying out sputtering of metals, has promptly plated the random copolymers film of metal level.This random copolymers its surface tension performance (wetting index) after the film surface corona is handled as the metal cladding film is at least 50mN/m (50dyn/cm (dynes per centimeter)).Better the wetting index of this random copolymers is 60mN/m (60dyn/cm) at least.The surface tension properties (behind corona discharge) that should be pointed out that homopolymer thin films is generally 40-42mN/m (40～42dyn/cm).
The sputtering of metals of the random copolymer composition of first specific embodiments of the present invention can realize with any known sputtering of metals method, such as corona discharge or vacuum metallizing.Can carry out Corona discharge Treatment along its surface for the treatment of spraymetal to this polymeric film, be placed on spraymetal in the vacuum then.This Corona discharge Treatment can be carried out at the appropriate time after random copolymers is shaped, but better is that this certain point between film shaped and film batch carries out the sputtering of metals processing.
Better should be able to obtain the wetting index of 50mN/m (50dyn/cm) at least when carrying out this Corona discharge Treatment, and serve as better with 55mN/m (55dyn/cm) at least.Randomly, adopt a kind of adhesive means to strengthen the bounding force between random copolymers film and the required metal.Suitable adhesive means comprises polyester, urethane and Resins, epoxy.Adhesive means can be applied on the surface of the random copolymers film that will carry out Corona discharge Treatment.Certainly, this adhesive means can side by side adopt with sputtering of metals.
Any known vacuum metallizing method all can adopt, and generally uses a kind of equipment of sending into part, sputtering of metals part and winding part that has film.Work can be reduced to the barometric point of device interior in the time of by oil pump and diffusion pump, for example, and about 1CPa (10
-4Torr) even lower.Treat matel coated such as aluminium with being equipped with in one, or contain and remain the container heating of metal-coated long filament, make metal melting and this evaporation of metal.The metallic molecule of evaporation is deposited on the film surface of sending into continuously, then reels.The thickness of metal plating is generally between 0.01～several microns.
Second specific embodiments of the present invention relates to a kind of polymer composition, it is made up of following: (1) accounts for most isotactic random copolymer, this multipolymer is gone up substantially by 0.8%～20%, better 5%～18%, better 7%～14.5%, and the butene-1 unit and 80%～99.2% (weight) of best 7.5%～10.0% (weight) the better propylene units of 82%-95% is formed; And (2) are at least a enhances the transparency/glossy soft silica anti.The polymeric articles of producing, i.e. film usually has at least 8% transparency (measuring according to ASTM D-1746) and 129～145 glossiness (60 °).(measuring) according to ASTM D-523.Randomly, this polymer composition comprises the additive-package that can reduce yellowing.This synthetic soft silica can have flaky form usually, between the higher bulk density of 300～360g/l scope and between the low oil absorption rate of 80～100g/100g scope.The consumption of this synthetic amorphous silicon oxide anti is 0.05%～0.35% (weight) of copolymer compositions weight, better 0.07%～0.25% (weight), and 0.10～0.20% is better, is best with 0.13～0.17% (weight).
A concrete aspect according to second specific embodiments of the present invention, this polypropylene random copolymer composition comprises a kind of additive-package, wherein contain the four [methylene radical (3 that account for composition weight 0.03%～0.10%, 5-di-t-butyl-4-hydroxyl hydrogenation cinnamic ester)] methane, 0.05%～0.11% two (2,4-two-tertiary butyl-phenyl) pentaerythritol diphosphites and 0.01%～0.04% hydroxide carbonic acid magnalium hydrate, every kind of quantity is benchmark with the total copolymer composition weight all.
The polymer composition of second specific embodiments preferably has the one or more features in following (A)～(I):
(A) extension at break (press ASTM D 882 measure), 400%～2000%, more fortunately 600%～1500%, serving as better in 700%～1400% scope;
(B) hexane extraction thing content (measuring) 50 ℃ the time by 21 C.F.R. § 177.1520 (c) (3.1 and 3.2), at the most 5.5%, better 3.5%, at least 2.6% better at the most, and 2.0% being best at the most;
(C) xylene solubles level (measuring) 23 ℃ the time by 21 C.F.R.177.1520, at the most 13%, better at the most 6%, 5% serve as better at the most, and 3% be best at the most;
(D) the anti-mould degree of opening (is pressed ASTM D 882 (1% secant is measured with 0.13cm/ branch (speed of 0.05 inch per minute)), at least 2812kg/cm
2(40,000psi), better 4218kg/cm at least
2(60,000psi), with 5625kg/cm at least
2(80, be better 000psi), and 7031kg/cm at least
2(100, modulus 000psi) is best;
(E) mist degree (press ASTM D-1003 measure), at the most 5%, so that 3% mist degree is better at the most, 2.5% mist degree is better at the most; Mist degree is the tolerance of film opacity or turbidity;
(F) gloss (pressing ASTM D-523 (60 °) measures) in 129～145 scopes, serves as better between 131～144, serves as better (gloss is relevant with the light or the flash of light degree of film) between 136～142.5;
(G) yellowness index of pelletizing (press ASTM D 1925 measure) is at most-1.2, better at the most-0.5, serve as better at the most-0.1, and 0.05 is best at the most;
(H) transparency (pressing ASTM D-1746 measures), at least 8%, the transparency with at least 11% serves as better, and at least 13% transparency is best.Higher transparency numerical value correspondence when seeing through can see more clearly object image when film is observed.Transparency be when passing film scattering less than the tolerance of light of 0.1 degree; And
(I) frictional coefficient (COF), comprise static with dynamically (press ASTM D-1894 mensuration), at the most 0.30, serve as better with 0.20 COF at the most.
When adopting typical vapor phase process to produce, polymer composition as described above, its melt flow (by traditional test determines, ASTM-1238 for example, condition L) is 0.8dg/min～50dg/min.Melt flow in 1dg/min～25dg/min scope is relatively good, and 3dg/min～20dg/min is better.
As a concrete aspect of second specific embodiments of the present invention, polymer composition is contacted with superoxide for example being higher than under 180 ℃ the high temperature.This processing is referred to as " visbreaking ", and its method then belongs to the known technology scope.Visbreaking can be used for improving as requested the melt flow of reactor polymer product.
Just obtain visbroken polymers product of the present invention by the polymer composition visbreaking of the present invention that melt flow is at least 0.8dg/min.The visbreaking product that generates is 2 with the melt flow ratio of the starting polymer product of visbreaking not at least, and better melt flow ratio is 5, serves as better to equal 8 melt flow ratio.
The feature of the polymer composition of second specific embodiments of the present invention and visbreaking derivative thereof is the excellent balance between improved low hexane extract, good gloss, good transparency, low yellowness index and the low haze.
This based composition can adopt traditional method that is used for thermoplastic material, and for example extrusion molding, injection moulding and thermoforming and relevant technology are processed.In the middle of the concrete application of this composition, orientation or the not production of oriented film of adopting curtain coating or film inflation method are arranged.After the shaping, can by the heat seal anchor clamps under predetermined temperature, pressure and pressing time condition with the film heat seal.The film that generates has low heat seal initial temperature, low hexane extract and improved optical property, as high-clarity, high gloss and low yellowness index.
Suitable synthetic soft silica antiblocking additive comprises Gasil
AB 720 (by Crosfield Group of Warrington, England provides).On the contrary, inapplicable a kind of traditional soft silica is Sylobloc 48 (a W.R.Grace company) usually; It typically has the bulk density of 128g/l and the oil absorption rate of 220g/100g, has the spheroidal particle form.
Copolymer compositions of the present invention can randomly comprise additive, as processing stabilizers, oxidation inhibitor, UV stabilizer, pigment, acid neutralizing agent (as hydroxide carbonic acid magnalium hydrate), acid acceptor, surface slip agent (as erucicamide), nucleator, releasing agent, dispersion agent, acid (may not exist), antiblocking agent (for example soft silica), as long as these additives do not have adverse influence to composition favorable optical performance and low yellowness index, they are exactly the additive that is used for the commercial polymer composition traditionally.
The example of operable processing stabilizers comprises two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, four (2, the 4-di-tert-butyl-phenyl) 4-4 '-biphenylene diphosphites (diphosphonite), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; Oxidation inhibitor, as 3-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, four [methylene radical (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate)] methane, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates, tetramethylolmethane-four-(β-lauryl thiopropionate) and distearylthiodi-propionate.
Typical UV stabilizer comprises 2-hydroxyl-4-n-octyloxy-benzophenone, 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-5-chlorobenzene triazole, the ethanol condensed thing of Succinic acid dimethylester-2-(4-hydroxyl-2,2,6,6-tetramethyl--piperidino).
Typical acid acceptor is Hydrotalcile DHT-4A, calcium stearate and calcium lactate.
Invention described herein is specified by following illustrative embodiment and Comparative Examples, but not limited thereto.In all illustrative embodiment and Comparative Examples, used following term;
SCA (selective control agent)
NPTMS (n-propyl Trimethoxy silane)
PEEB (ethyl p-ethoxybenzoate)
Illustrative embodiment I
A). the preparation of raw catalyst
In the titanium tetrachloride of 2953 L 50/50 (volume) and chlorobenzene solution, add 50kg diisobutyl phthalate and 231kg carbonization magnesium ethylate in succession.Holding temperature is at 20 ℃～25 ℃ during the interpolation.Then, under agitation with the mixture heating up to 110 that generates ℃ and kept 1 hour.This time filters mixture when finishing while hot.Collect solid matter.
Then, the solution of at room temperature solid matter being put into 2953 L 50/50 (volume) titanium tetrachlorides and chlorobenzene carries out pulp.Under agitation the slurry that generates is heated to 110 ℃ then, and under this temperature, kept 60 minutes.This time filters mixture when finishing while hot.Collect solid matter.
This solid matter is placed on pulp once more in 2953 L 50/50 (volume) solution.The slurry that generates under agitation is heated to 110 ℃, and kept this temperature 30 minutes, this time is when finishing, with the mixture filtered while hot.Collect solid matter.
Residue is once dry under nitrogen purging then with the iso-pentane washing of 25 ℃ of 2271 L.
B). polymerization
The raw catalyst of steps A is made into 30% (weight) dispersion liquid in mineral oil, joins in the gas-phase fluidized-bed reactor continuously.Meanwhile and continuously in this reactor, add triethyl aluminum and selective control agent (" SCA "=NPTMS).To the molecular weight of the hydrogen of wherein introducing capacity with the adjusting polymerisate.Also there is a spot of nitrogen.Partial pressure of propylene is about 965KPa (140psi)～about 380psi.Polymerization temperature is 65 ℃, and the residence time is 1.5～2 hours.
Illustrative embodiment II
The preparation of raw catalyst
In the solution of 3558 L 50/50 (volume) titanium tetrachlorides and chlorobenzene, add 51kg diisobutyl phthalate and 150kg diethoxy magnesium in succession.Temperature maintenance is at 20 ℃～25 ℃ between this charge period.Under agitation the mixture heating up to 110 that generates ℃, under this temperature, kept 1 hour then.This time is when finishing, with the mixture filtered while hot.Collect solid matter.
Then, at room temperature this solid matter is placed in the solution of 3558 L 50/50 (volume) titanium tetrachlorides and chlorobenzene and carries out pulp.Then the slurry that generates under agitation is heated to 110 ℃, kept this temperature 60 minutes.When this finishes time with the mixture filtered while hot.Collect solid matter.
This solid matter is placed in the solution of 3558 L 50/50 (volume) and carries out pulp once more.Under agitation the slurry with this generation is heated to 110 ℃, and keeps this temperature 30 minutes.When finishing, this time, collects solid matter with the mixture filtered while hot.
The 25 ℃ iso-pentane of this residue with every part 3785 L are washed four times, dry under nitrogen purging then.
B). polymerization
The dispersion liquid that the raw catalyst of steps A is made into 30% (weight) in mineral oil joins in the fluidized-bed reactor continuously.In this reactor, add simultaneously 5% (weight) triethyl aluminum solution and 0.5～5% selective control agent (" SCA "=NPTMS) solution in iso-pentane in iso-pentane continuously.The hydrogen of introducing capacity is to regulate the molecular weight of polymerisate.Also there is a spot of nitrogen.Partial pressure of propylene is about 956KPa (140psi)～about 2068KPa (300psi), and polymerization temperature is 65 ℃ or 80 ℃, and the residence time is 2 hours～about 4 hours.
Comparative Examples I
Repeated the used same program of illustrative embodiment I, just replaced butene-1 with ethene.A series of polymeric the results are shown in table 1 and 2.
Comparative Example II
(a) preparation of raw catalyst component
By chlorobenzene/TiCl at 150ml 50/50 (volume)
4Add the diethoxy magnesium of 50mmol in the mixture, make raw catalyst.Add ethyl benzoate (16.7mmol) afterwards, place mixture oil bath to heat, and, then mixture is filtered 110 ℃ of following stir abouts 30 minutes.With slurry with the iso-pentane of every part of 150ml washing six times, under 30 ℃ and condition of nitrogen gas dry 90 minutes then.
(b) polymerization
(step a) makes propylene and vinyl polymerization by described the same manner of step (b) of illustrative example I, and that just selective control agent adopts is PEEB with above-mentioned raw catalyst.
Comparative Example II I
With the raw catalyst of illustrative embodiment I (a), by making propylene polymerization like that described in the illustrative example I (b).
The flat film that is extruded into as the described all thickness of illustrative embodiment III of the copolymer products that obtains from Comparative Examples 1, II and III.The result is stated from table 1 and 2.
Illustrative embodiment III
The film cast of polymer product
Use conventional methods some are reclaimed according to the polypropylene product that illustrative embodiment I, II and Comparative Examples I, II and III produce.Some are reclaimed product mixes with one of following additive-package:
A) Irganox of 1000ppm
1010 hindered phenol primary antioxidants (providing), 1000ppm Irgafos by Ciba Geigy company
168 phosphite type auxiliary anti-oxidants (CibaGeigy company), 400ppm Hydrofalcite DHT-4A acid neutralizing agent (KyowaChemical Industry).
(B) 500ppm Irganox
1010,800ppm Ultranox
626 and phosphite type auxiliary stabilizer (providing) and 200ppm Hydrotalcite DHT-4A by General Electric Specialty Chemicals.
After will reclaiming product and one of above-mentioned additive-package being mixed.With the superoxide of capacity is wished the mixture visbreaking of part generation with acquisition melt flow, pelletizing then.
To cut granulated polymer product (visbreaking or not visbreaking) and be extruded into film according to follow procedure is flat: 6.3cm (
Inch) (L/D=24: 1) melt temperature of going up with 250 ℃ is extruded into the thick sheet material of 0.13cm (0.05 inch) with pelletizing to the forcing machine of diameter, and the about 100rpm of its speed, head pressure are 13790KPa (2000psi).The chill roll of wide template of 30.5cm (12 inches) and 33cm (13 inches) diameter and the water-bath that temperature is 25 ℃ have been adopted.After sheet cools, it is placed on machine direction orientation (MDO) the section reheat of 120 ℃ of roller temperature, and stretches with 5.5: 1 multiples.Allow sheet material pass through horizontal orientation (TDO) section, wherein the preheating section temperature is that 175 ℃, drawing zone temperature are that 160 ℃ and annealed zone temperature are 162 ℃.With sheet material along laterally stretching with 8: 5: 1 stretch ratio.
" melt temperature " (℃) be that differential scanning calorimetric curve by each product polymkeric substance of producing draws.
Measure other performances of random copolymer composition as follows:
Elongation (%) ASTM D 638 (23 ℃)
Melt flow ASTM D 1238.78, condition L
Mist degree ASTM D 1003
Gloss (60 ° time) ASTM D 2457
Modulus is (at 0.13cm/ branch (0.05 inch per minute)
The time 1% secant)
ASTM D 790A
Tensile strength at break ASTM D 638
A series of polymeric the results are shown in table 1 and 2.
Table 1
A. press the homopolymer composition of Comparative Example II preparation.B. by the butene random that contains 1% butylene of illustrative example II preparation.C. press the visbreaking homopolymer of Comparative Example II I preparation.D. press the homopolymer composition of Comparative Example II I preparation.E. by the ethylene random that contains 0.5% ethene of Comparative Examples I preparation.F. (in the bracket film thickness of mil (0.001 inch) expression with mm.
| Specimen coding | Thickness f(mm) | Tangent modulus (* 1000kg/cm 2) (×1000psi) | Tensile strength at break (* 1000kg/cm 2) (×1000psi) | Extension at break (%) | Mist degree | Gloss (60 °) | |||
| MD | TD | MD | TD | MD | TD | ||||
| 1 a | 0.020 (0.8) | 29.08 (413.6) | 74.03 (1053.0) | 1.31 (18.7) | 4.30 (61.2) | 151 | 27 | 0.7 | 137.3 |
| 2 b | 0.022 (0.9) | 26.53 (377.4) | 58.51 (832.2) | 1.39 (19.7) | 3.36 (47.8) | 138 | 28 | 0.2 | 150.0 |
| 3 c | 0.022 (0.9) | 26.27 (373.7) | 67.83 (964.8) | 1.43 (20.3) | 3.82 (54.3) | 148 | 28 | 0.1 | 147.1 |
| 4 d | 0.020 (0.8) 0.018 (0.7) | 25.73 (365.9) | 66.95 (952.2) | 1.44 (20.5) | 3.92 (55.8) | 145 | 28 | 0.4 | 141.6 |
| 5 e | 0.020 (0.8) | 25.61 (364.3) | 66.50 (945.8) | 1.49 (21.2) | 3.89 (55.3) | 155 | 28 | 0.6 | 146.6 |
D. press the alfon of Comparative Example II I preparation.</entry></row></tbody></tgroup></table></tables>
Illustrative embodiment IV
The polymer reactor product that a part is produced according to illustrative embodiment I (propene/but-1-ene-1 random copolymers wherein contain the butene-1 of about 7% (weight), and the multipolymer melt flow is 3.4 (press ASTM D 1238, condition L measures)) and by Irganox
1010 (500ppm) phenols primary antioxidant (providing), Ultranox by Ciba Geigy company
626 phosphorous acid esters assist stablizer (providing) by General Electric Specialty Chemicals (800ppm), Hydrotalcite DHT-4A acid neutralizing agent (200ppm) (providing), Kemamide by Kyowa Chemical Industry
The additive-package that one of E erucicamide (100ppm) (being provided by Witco company) and following antiblocking agent are formed is mixed and pelletizing;
(A) SYLOBLOC
48 silicon-dioxide antiblocking agents (traditional silicon dioxide that provides by W.R.Grace).
(B) GASIL
Soft silica anti (being provided by Crosfield) is provided AB720.The mean particle size of every kind of silicon-dioxide is about 4 microns.
Mixing is to have in 11/4 inch Brabender extruding machine of Maddock mixing screw, finishes under nitrogen and 250 ℃ of melt temperature conditions.
Pelletizing is extruded into the thick casting films of 0.089mm (3.5 mil), employing be to have 1.9cm (3/4 inch) the Brabender extruding machine (200 ℃ of melt temperatures) of the wide template of 20.3cm (8 inches) and the Killion chill roll (15 ℃) of 25.4cm (10 inches).All identical to the used operational condition of all polymer compositions.The test result of the film of producing is stated from table 3.
2. the polymer composition that comprises the anti A of illustrative embodiment IV.4. frictional coefficient.5. pelletizing is recorded.</entry></row></tbody></tgroup></table></tables>
As what see from table 3, to compare with the polymeric film that adopts antiblocking additive A, the polymer thin film composition that adds various horizontal antiblocking additive B all shows high-clarity and higher gloss.It can also be seen that the pelletizing that is made of the composition that adopts anti B shows to the pelletizing of adopting antiblocking additive A has similar yellowness index.
Illustrative embodiment V
Mixing as follows the prescription of table 4.Base resin is the propene-1-butene random copolymers, its nominal melt flow be 1.5 and butene monomers content be 7.5% (weight).With this Kemamide of stabilization powder and 0.05% (weight) Irganox 1010,0.08% (weight) Ultranox626,0.02% (weight) Hydrotalcite DHT-4A, 0.15% (weight) anti (Gasil AB 720 or be used for correlated Sylobloc 48) and variable level not
E (erucicamide) surface slip agent is mixing together.It in all prescriptions chemically to melt flow (MF) 8 particle with powder cracking (or degrade) with Lupersol101 superoxide (250ppm).Mixing be the 3.17cm that has the Maddock mixing screw (
Inch) in the Brabender extruding machine.Under the condition of nitrogen and 230 ℃ of melt temperatures and 100rpm screw speed, finish.
Adopt 1.90cm (3/4 inch) Brabender extruding machine, under the Killion chill roll condition of 234 ℃ of melt temperatures, 65rpm screw speed, 20.3cm (8 inches) wide slit template and 15 ℃, pelletizing is extruded into 100 microns (4 mil) thick casting films.
Table 4 has provided the performance of the film of producing.The film that has added Gasil AB 720 demonstrates than high transparency of the film that adds Sylobloc 48 and high gloss.Equally, under the condition of given surface slip agent content, the film that has added Gasil AB 720 demonstrates than the low frictional coefficient (COF) of film that adds Sylobloc 48.COF is low just to mean that the slip additive requirement is few.This is favourable, because incrustation and template settling in the operation of surface slip agent content higher meeting causing film extrusion.
Table 4
1. the ppm2. of surface slip agent (erucamide) adds the polymer composition of Sylobloc 48 antis (1500ppm).3. the polymer composition that adds Gasil AB 720 antis (1500ppm).4. frictional coefficient (metal pair film).
| Surface slip agent ppm 1 | 0 | 500 | 1000 | 1500 | 2000 |
| A 2 B 3 | A 2 B 3 | A 2 B 3 | A 2 B 3 | A 2 B 3 | |
| COF 4-static-dynamically | 0.342 0.322 0.342 0.354 | 0.328 0.299 0.307 0.270 | 0.264 0.219 .207 0.182 | 0.219 .206 .163 .150 | 0.192 0.170 0.135 0.118 |
| Mist degree (%) | 1.2 1.4 | 1.1 1.4 | 1.2 1.9 | 1.2 1.5 | 1.2 1.5 |
| Transparency (%) | 6.8 11.3 | 6.9 10.7 | 14.9 17.9 | 7.5 8.4 | 9.7 10.1 |
| Gloss (60 °) | 124.6 142.3 | 127.5 143.4 | 137.8 139.9 | 135.6 141.0 | 133.8 142.4 |
Find out further that from table 3 and 4 flaky silicon dioxide gives film the frictional coefficient low than traditional silicon dioxide.
Claims (17)
1. polymer composition, wherein comprise a kind of random copolymers that (1) contains 0.5%～20% (weight) butene-1 and 80% (weight)～99.5% (weight) propylene, and (2) account for the synthetic soft silica antiblocking agent of polymer composition 0.05%～0.35% (weight); The bulk density of wherein said synthetic soft silica antiblocking agent is 300～360g/l, and its oil absorption rate is 80～100g/100g; Wherein the said polymer composition has following feature:
(a) hexane extraction thing 50 ℃ the time, at the most 5.5%,
(b) mist degree, at the most 5%,
(c) xylene solubles thing level 23 ℃ the time is the highest by 13%,
(d) tensile modulus, 2812kg/cm at least
2(40,000psi), and
(e) extension at break, 80%～2000%.
2. the polymer composition of claim 1, wherein the said polymer composition comprises the said synthetic soft silica of 0.05～0.35 (weight), and wherein said composition has:
(a) greater than 8% transparency; And
(b) gloss in the time of 60 ° is 129～145.
3. according to the polymer composition of claim 2, wherein said random copolymers comprises 5%～18% (weight) butene-1 and 82%～95% (weight) propylene.
4. according to the polymer composition of claim 1, wherein butene-1 accounts for 0.5%～6.5% of random copolymers weight.
5. according to the polymer composition of claim 4, wherein the tensile strength of composition is 1195kg/cm at least
2(17,000psi), the hexane extraction thing is 2.6% at the most in the time of its 50 ℃, and mist degree is up to 3%, and the xylene soluble part level 23 ℃ the time the highest be 6.0%.
6. according to the polymer composition of claim 4, wherein said composition contains the said synthetic soft silica of 0.07%～0.25% (weight).
7. according to any one polymer composition in the claim of front, wherein random copolymers is the copolymer that is made of butene-1 and propylene.
8. according to claim 1,2,3,4,5 or 6 polymer composition, wherein said random copolymers prepares by a kind of method, this method is included in propylene is contacted with the catalyst system that contains magnesium, titanium with butene-1, and this system is by allowing raw catalyst, (b) organoaluminum promotor of (a) titaniferous, magnesium contact with (c) organosilane selective control agent and to obtain.
9. according to claim 1,2,3,4,5 or 6 polymer composition, wherein at least a portion random copolymers is the visbreaking random copolymers, it is to produce the melt flow polymer materials of 1.5dg/min at least by allowing propylene and butene-1 contact with the catalyst system that contains magnesium, titanium under polymerizing condition, with the polymer materials visbreaking of said generation, 1.5 make at least again down to the random copolymers of this visbreaking and the melt flow ratio of this polymer materials.
10. according to claim 1,2,3,4,5 or 6 polymer composition, wherein at least a portion random copolymers is the visbreaking random copolymers, it is to produce the melt flow polymer materials of 0.8dg/min at least by allowing propylene and butene-1 contact with the catalyst system that contains magnesium, titanium under polymerizing condition, with the polymer materials visbreaking of said generation, 2 make at least again down to the random copolymers of this visbreaking and the melt flow ratio of this polymer materials.
11. according to claim 1,2,3,4,5 or 6 polymer composition, wherein said composition further comprises a kind of additive-package, wherein comprises to be selected from least a in one group that is made of oxidation inhibitor, UV stabilizer, pigment, dispersion agent, surface slip agent, neutralizing agent, nucleator, processing stabilizers and releasing agent.
12. according to claim 1,2,3,4,5 or 6 polymer composition, wherein said polymer composition further comprises at least a additive, it is selected from by four [methylene radical (3,5-di-t-butyl-4-hydroxyl hydrogenation cinnamic ester)] group of methane, two (2,4-di-t-butyl-phenyl) pentaerythritol diphosphites, erucicamide and hydroxide carbonic acid magnalium hydrate formation.
13. a film that comprises according to claim 4,5 or 6 polymer composition, it is orientated.
14. a film wherein comprises orientation bottom and (2) polymer layer on the one side at least of this bottom that (1) is made of the film according to claim 13.
15. according to the film of claim 14, wherein polymer layer is to be transformed by propene-1-butene-1 multipolymer that contains 7%～15% (weight) butene-1.
16. by the film that metal plating is arranged or the sheet material that obtain according to claim 4,5 or 6 polymer composition.
17. the film that metal plating is arranged or the sheet material of claim 16, wherein the wetting index after the sputtering of metals is 50N/m (50dyn/cm) at least.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15778793A | 1993-11-23 | 1993-11-23 | |
| US16155293A | 1993-11-23 | 1993-11-23 | |
| US157,787 | 1993-11-23 | ||
| US161,552 | 1993-11-23 | ||
| US157787 | 1993-11-23 | ||
| US161552 | 1993-11-23 |
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| CN1085700C true CN1085700C (en) | 2002-05-29 |
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| Country | Link |
|---|---|
| EP (1) | EP0730623B1 (en) |
| JP (1) | JP3025016B2 (en) |
| CN (1) | CN1085700C (en) |
| AT (1) | ATE163665T1 (en) |
| AU (1) | AU690611B2 (en) |
| BR (1) | BR9408130A (en) |
| CA (1) | CA2177082C (en) |
| DE (1) | DE69408864T2 (en) |
| ES (1) | ES2116064T3 (en) |
| WO (1) | WO1995014738A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG48689A1 (en) * | 1995-06-02 | 2001-04-17 | Union Carbide Chem Plastic | Random copolymer compositions |
| US5922471A (en) * | 1996-03-04 | 1999-07-13 | Union Carbide Chemicals & Plastics Technology Corporation | Metallizable polypropylene random copolymer compositions |
| KR100387733B1 (en) * | 1999-08-12 | 2003-06-18 | 삼성종합화학주식회사 | Aluminum plated polypropylene composition |
| GB0130907D0 (en) | 2001-12-22 | 2002-02-13 | Ineos Silicas Ltd | Amorphous silica |
| SG150519A1 (en) * | 2007-02-01 | 2009-03-30 | Sumitomo Chemical Co | Propylene-based copolymer material, film made therefrom, and method for producing propylene-based copolymer material |
| US8129490B2 (en) * | 2007-05-22 | 2012-03-06 | Basell Poliolefine Italia S.R.L. | Soft propylene polymer compositions |
| CN102234399A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | Foot packaging container and manufacturing method thereof |
| CN102453282A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
| CN102453283A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
| KR101773487B1 (en) * | 2011-10-29 | 2017-08-31 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Propylene random copolymer, method for its preparation, and compositions and articles containing the same |
| JP6203405B2 (en) * | 2013-12-18 | 2017-09-27 | ボレアリス エージー | BOPP film with improved stiffness / toughness balance |
| CN108623917B (en) * | 2017-03-23 | 2021-03-23 | 中国石油化工股份有限公司 | Polypropylene composition, preparation method thereof and polymer film |
| BR112019020838B1 (en) | 2017-04-04 | 2023-12-12 | Braskem America, Inc | Low opacity film, packaging composition, plastic composition, and method for preparing the low opacity film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU7410891A (en) * | 1990-04-06 | 1991-10-10 | Novolen Technology Holdings C.V. | Copolymers of propylene with other 1-alkenes |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2105651B (en) * | 1978-06-14 | 1983-09-01 | Sumitomo Chemical Co | Multi-layer polypropylene film |
| JPS5911249A (en) * | 1982-07-09 | 1984-01-20 | 住友化学工業株式会社 | Polypropylene group resin film for evaporating aluminum |
| JPH0668050B2 (en) * | 1989-06-28 | 1994-08-31 | チッソ株式会社 | Polypropylene resin composition for metal deposition film |
| JP3050937B2 (en) * | 1991-03-15 | 2000-06-12 | 水澤化学工業株式会社 | Amorphous silica filler |
| CA2098664A1 (en) * | 1992-06-30 | 1993-12-31 | Hajime Sadatoshi | Polypropylene random copolymer and film thereof |
-
1994
- 1994-11-18 ES ES95902594T patent/ES2116064T3/en not_active Expired - Lifetime
- 1994-11-18 AT AT95902594T patent/ATE163665T1/en not_active IP Right Cessation
- 1994-11-18 CA CA002177082A patent/CA2177082C/en not_active Expired - Fee Related
- 1994-11-18 BR BR9408130A patent/BR9408130A/en not_active Application Discontinuation
- 1994-11-18 EP EP95902594A patent/EP0730623B1/en not_active Expired - Lifetime
- 1994-11-18 CN CN94194174A patent/CN1085700C/en not_active Expired - Fee Related
- 1994-11-18 DE DE69408864T patent/DE69408864T2/en not_active Expired - Fee Related
- 1994-11-18 WO PCT/US1994/013309 patent/WO1995014738A1/en active IP Right Grant
- 1994-11-18 AU AU11811/95A patent/AU690611B2/en not_active Ceased
- 1994-11-18 JP JP7515147A patent/JP3025016B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU7410891A (en) * | 1990-04-06 | 1991-10-10 | Novolen Technology Holdings C.V. | Copolymers of propylene with other 1-alkenes |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2177082A1 (en) | 1995-06-01 |
| WO1995014738A1 (en) | 1995-06-01 |
| JP3025016B2 (en) | 2000-03-27 |
| ES2116064T3 (en) | 1998-07-01 |
| AU1181195A (en) | 1995-06-13 |
| BR9408130A (en) | 1997-08-05 |
| AU690611B2 (en) | 1998-04-30 |
| JPH09509192A (en) | 1997-09-16 |
| EP0730623A1 (en) | 1996-09-11 |
| DE69408864T2 (en) | 1998-06-25 |
| CN1147827A (en) | 1997-04-16 |
| CA2177082C (en) | 2002-03-12 |
| ATE163665T1 (en) | 1998-03-15 |
| DE69408864D1 (en) | 1998-04-09 |
| EP0730623B1 (en) | 1998-03-04 |
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